JP2021004405A - Electrical contact material, terminal metal fitting, connector, wire harness, and method of producing electrical contact material - Google Patents

Electrical contact material, terminal metal fitting, connector, wire harness, and method of producing electrical contact material Download PDF

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JP2021004405A
JP2021004405A JP2019119508A JP2019119508A JP2021004405A JP 2021004405 A JP2021004405 A JP 2021004405A JP 2019119508 A JP2019119508 A JP 2019119508A JP 2019119508 A JP2019119508 A JP 2019119508A JP 2021004405 A JP2021004405 A JP 2021004405A
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metal layer
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electrical contact
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JP7333010B2 (en
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善晶 白井
Yoshiaki Shirai
善晶 白井
齋藤　寧
Yasushi Saito
寧 齋藤
古川　欣吾
Kingo Furukawa
欣吾 古川
充弘 公文代
Mitsuhiro Kumondai
充弘 公文代
細江　晃久
Akihisa Hosoe
晃久 細江
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Sumitomo Wiring Systems Ltd
AutoNetworks Technologies Ltd
Sumitomo Electric Industries Ltd
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Sumitomo Wiring Systems Ltd
AutoNetworks Technologies Ltd
Sumitomo Electric Industries Ltd
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Priority to JP2019119508A priority Critical patent/JP7333010B2/en
Priority to US16/897,356 priority patent/US11228127B2/en
Priority to DE102020003784.4A priority patent/DE102020003784A1/en
Priority to CN202010587200.7A priority patent/CN112151991A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/02—Alloys based on zinc with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0607—Wires
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
    • H01R43/16—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors for manufacturing contact members, e.g. by punching and by bending
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/10—Sockets for co-operation with pins or blades
    • H01R13/11—Resilient sockets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
    • H01R4/10—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation effected solely by twisting, wrapping, bending, crimping, or other permanent deformation
    • H01R4/18—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation effected solely by twisting, wrapping, bending, crimping, or other permanent deformation by crimping
    • H01R4/183—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation effected solely by twisting, wrapping, bending, crimping, or other permanent deformation by crimping for cylindrical elongated bodies, e.g. cables having circular cross-section
    • H01R4/184—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation effected solely by twisting, wrapping, bending, crimping, or other permanent deformation by crimping for cylindrical elongated bodies, e.g. cables having circular cross-section comprising a U-shaped wire-receiving portion
    • H01R4/185—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation effected solely by twisting, wrapping, bending, crimping, or other permanent deformation by crimping for cylindrical elongated bodies, e.g. cables having circular cross-section comprising a U-shaped wire-receiving portion combined with a U-shaped insulation-receiving portion

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)
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  • Manufacturing Of Electrical Connectors (AREA)

Abstract

To provide an electrical contact material capable of suppressing an increase in contact resistance even if a contact pressure against an opposite material is small.SOLUTION: The electrical contact material comprises a base material made of metal, a metal layer disposed on the surface of the base material, and an oxide layer disposed on the surface of the metal layer, with the metal layer made of metal including zinc, copper, and stannum, the oxide layer made of oxides including zinc, copper and stannum, and the ratio of an atomic concentration of copper relative to an atomic concentration of stannum at a position directly below the oxide layer being lower than 1.4.SELECTED DRAWING: Figure 1

Description

本開示は、電気接点材料、端子金具、コネクタ、ワイヤーハーネス、及び電気接点材料の製造方法に関する。 The present disclosure relates to electrical contact materials, terminal fittings, connectors, wire harnesses, and methods for manufacturing electrical contact materials.

特許文献１には、金属材料からなる基材と、基材上に形成された合金層と、合金層の表面に形成された導電性皮膜層（酸化物層）とを備えるコネクタ用電気接点材料が開示されている。合金層は、Ｓｎ及びＣｕを必須元素として含み、かつＺｎ、Ｃｏ、Ｎｉ、及びＰｄから選択される１種又は２種以上の添加元素（Ｍ）を含む。また、合金層は、Ｃｕ６Ｓｎ５で示される金属間化合物のＣｕを上記添加元素（Ｍ）に置換してなる（Ｃｕ，Ｍ）６Ｓｎ５で示される金属間化合物を含む。酸化物層は、合金層の構成元素が酸化されて形成される。 Patent Document 1 describes an electrical contact material for a connector including a base material made of a metal material, an alloy layer formed on the base material, and a conductive film layer (oxide layer) formed on the surface of the alloy layer. Is disclosed. The alloy layer contains Sn and Cu as essential elements, and also contains one or more additive elements (M) selected from Zn, Co, Ni, and Pd. Further, the alloy layer contains the intermetallic compound represented by (Cu, M) 6 Sn 5 obtained by substituting the Cu of the intermetallic compound represented by Cu 6 Sn 5 with the additive element (M). The oxide layer is formed by oxidizing the constituent elements of the alloy layer.

特開２０１５−６７８６１号公報JP 2015-67861

電気接点材料の最表面に形成される酸化物層は、接触抵抗を上昇させ得る。しかし、この酸化物層は、電気接点材料の使用時における相手材との嵌合によって荷重が加わることで破壊され易い。酸化物層が破壊されることで、電気接点材料における接触抵抗の上昇を抑制でき、合金層を介して電気接点材料と相手材との間で良好な電気的接続を確保し易い。これは、破壊された酸化物層から露出される電気接点材料の新生面に相手材が接触できるからである。 The oxide layer formed on the outermost surface of the electrical contact material can increase the contact resistance. However, this oxide layer is liable to be broken by applying a load due to fitting with the mating material when the electrical contact material is used. By breaking the oxide layer, it is possible to suppress an increase in contact resistance in the electrical contact material, and it is easy to secure a good electrical connection between the electrical contact material and the mating material via the alloy layer. This is because the mating material can come into contact with the new surface of the electrical contact material exposed from the fractured oxide layer.

相手材との接触圧力が小さく、使用時に電気接点材料に加わる荷重が小さい場合であっても、相手材と良好な電気的接続を確保できる電気接点材料が求められている。例えば、コネクタの端子金具が従来に比較して小さくなると、相手材との接触圧力が小さくなり、使用時に電気接点材料に加わる荷重も小さくなる。電気接点材料に加わる荷重が小さくなると、酸化物層が破壊され難く、接触抵抗の上昇を引き起こし、相手材と良好な電気的接続を確保し難い。 There is a demand for an electrical contact material that can secure a good electrical connection with the mating material even when the contact pressure with the mating material is small and the load applied to the electrical contact material during use is small. For example, when the terminal fitting of the connector is smaller than before, the contact pressure with the mating material is reduced, and the load applied to the electrical contact material during use is also reduced. When the load applied to the electrical contact material is small, the oxide layer is not easily destroyed, the contact resistance is increased, and it is difficult to secure a good electrical connection with the mating material.

そこで、本開示は、相手材との接触圧力が小さい場合であっても、接触抵抗の上昇を抑制できる電気接点材料を提供することを目的の一つとする。また、本開示は、上記電気接点材料からなる端子金具、上記端子金具を備えるコネクタ、及び上記端子金具又はコネクタを備えるワイヤーハーネスを提供することを目的の一つとする。更に、本開示は、相手材との接触圧力が小さい場合であっても、接触抵抗の上昇を抑制できる電気接点材料を容易に得られる電気接点材料の製造方法を提供することを目的の一つとする。 Therefore, one of the objects of the present disclosure is to provide an electric contact material capable of suppressing an increase in contact resistance even when the contact pressure with the mating material is small. Another object of the present disclosure is to provide a terminal fitting made of the electrical contact material, a connector provided with the terminal fitting, and a wire harness provided with the terminal fitting or the connector. Further, one of the purposes of the present disclosure is to provide a method for manufacturing an electric contact material that can easily obtain an electric contact material capable of suppressing an increase in contact resistance even when the contact pressure with the mating material is small. To do.

本開示の電気接点材料は、
金属からなる基材と、
前記基材の表面に設けられる金属層と、
前記金属層の表面に設けられる酸化物層とを備え、
前記金属層は、亜鉛、銅、及びスズを含む金属からなり、
前記酸化物層は、亜鉛、銅、及びスズを含む酸化物からなり、
前記酸化物層の直下において、スズの原子濃度に対する銅の原子濃度の比率が１．４未満である。 The electrical contact material of the present disclosure is
A base material made of metal and
A metal layer provided on the surface of the base material and
It is provided with an oxide layer provided on the surface of the metal layer.
The metal layer is made of a metal containing zinc, copper, and tin.
The oxide layer is composed of oxides containing zinc, copper, and tin.
Immediately below the oxide layer, the ratio of the atomic concentration of copper to the atomic concentration of tin is less than 1.4.

本開示の端子金具は、本開示の電気接点材料からなる。 The terminal fittings of the present disclosure are made of the electrical contact material of the present disclosure.

本開示のコネクタは、本開示の端子金具を備える。 The connector of the present disclosure includes the terminal fitting of the present disclosure.

本開示のワイヤーハーネスは、
電線と、
前記電線に取り付けられる本開示の端子金具、又は本開示のコネクタとを備える。 The wire harness of the present disclosure is
With electric wires
The terminal fitting of the present disclosure attached to the electric wire or the connector of the present disclosure is provided.

本開示の電気接点材料の製造方法は、
基材の表面の少なくとも一部に、前記基材側から順に、第一層、第二層、及び第三層をめっきにより被覆した被覆材料を作製する工程と、
前記被覆材料に、酸素雰囲気中、２３２℃以上５００℃以下の温度で熱処理を施す工程とを備え、
前記被覆材料を作製する工程では、
前記第一層は、スズを含む金属からなり、
前記第二層は、亜鉛を含む金属からなり、
前記第三層は、銅を含む金属からなり、
前記第一層の厚さを３．５μｍ以上５μｍ以下、
前記第二層の厚さを０．１μｍ以上０．６μｍ以下、
前記第三層の厚さを０．０５μｍ以上０．４μｍ以下とする。 The method for manufacturing the electrical contact material of the present disclosure is as follows.
A step of producing a coating material in which the first layer, the second layer, and the third layer are coated by plating on at least a part of the surface of the base material in order from the base material side.
The coating material is provided with a step of heat-treating the coating material at a temperature of 232 ° C. or higher and 500 ° C. or lower in an oxygen atmosphere.
In the step of producing the coating material,
The first layer is made of a metal containing tin and
The second layer is made of a metal containing zinc and
The third layer is made of a metal containing copper.
The thickness of the first layer is 3.5 μm or more and 5 μm or less.
The thickness of the second layer is 0.1 μm or more and 0.6 μm or less.
The thickness of the third layer is 0.05 μm or more and 0.4 μm or less.

本開示の電気接点材料は、相手材との接触圧力が小さい場合であっても、接触抵抗の上昇を抑制できる。また、本開示の端子金具、コネクタ、及びワイヤーハーネスは、相手材との接触圧力が小さい場合であっても、接触抵抗の上昇を抑制できる。更に、本開示の電気接点材料の製造方法は、相手材との接触圧力が小さい場合であっても、接触抵抗の上昇を抑制できる電気接点材料を容易に得られる。 The electrical contact material of the present disclosure can suppress an increase in contact resistance even when the contact pressure with the mating material is small. Further, the terminal fittings, connectors, and wire harnesses of the present disclosure can suppress an increase in contact resistance even when the contact pressure with the mating material is small. Further, the method for producing an electric contact material of the present disclosure can easily obtain an electric contact material capable of suppressing an increase in contact resistance even when the contact pressure with the mating material is small.

図１は、実施形態に係る電気接点材料を示す概略構成図である。FIG. 1 is a schematic configuration diagram showing an electrical contact material according to an embodiment. 図２は、実施形態に係る電気接点材料の製造方法に関して、被覆材料を作製する工程を示す概略構成図である。FIG. 2 is a schematic configuration diagram showing a process of producing a coating material with respect to the method for producing an electrical contact material according to an embodiment. 図３は、実施形態に係る電気接点材料からなる端子金具を示す概略構成図である。FIG. 3 is a schematic configuration diagram showing a terminal fitting made of an electrical contact material according to an embodiment.

［本開示の実施形態の説明］
最初に本開示の実施形態の内容を列記して説明する。 [Explanation of Embodiments of the present disclosure]
First, the contents of the embodiments of the present disclosure will be listed and described.

（１）本開示の実施形態に係る電気接点材料は、
金属からなる基材と、
前記基材の表面に設けられる金属層と、
前記金属層の表面に設けられる酸化物層とを備え、
前記金属層は、亜鉛、銅、及びスズを含む金属からなり、
前記酸化物層は、亜鉛、銅、及びスズを含む酸化物からなり、
前記酸化物層の直下において、スズの原子濃度に対する銅の原子濃度の比率が１．４未満である。 (1) The electrical contact material according to the embodiment of the present disclosure is
A base material made of metal and
A metal layer provided on the surface of the base material and
It is provided with an oxide layer provided on the surface of the metal layer.
The metal layer is made of a metal containing zinc, copper, and tin.
The oxide layer is composed of oxides containing zinc, copper, and tin.
Immediately below the oxide layer, the ratio of the atomic concentration of copper to the atomic concentration of tin is less than 1.4.

本開示の電気接点材料は、酸化物層の直下におけるスズの原子濃度に対する銅の原子濃度の比率（以下、原子濃度比Ｃｕ／Ｓｎと呼ぶことがある）が１．４未満を満たすことで、酸化物層に銅の酸化物が形成され難い。銅の酸化物が少ない酸化物層は、低抵抗で導電性を確保し易い。そのため、本開示の電気接点材料は、金属層の表面に酸化物層が存在する状態であっても、相手材との間で良好な電気的接続を確保できる。よって、本開示の電気接点材料は、相手材との接触圧力が小さい場合であっても、接触抵抗の上昇を抑制できる。 The electrical contact material of the present disclosure satisfies that the ratio of the atomic concentration of copper to the atomic concentration of tin immediately below the oxide layer (hereinafter, may be referred to as the atomic concentration ratio Cu / Sn) is less than 1.4. It is difficult for copper oxide to be formed in the oxide layer. An oxide layer containing a small amount of copper oxide has low resistance and is easy to secure conductivity. Therefore, the electrical contact material of the present disclosure can secure a good electrical connection with the mating material even when the oxide layer is present on the surface of the metal layer. Therefore, the electrical contact material of the present disclosure can suppress an increase in contact resistance even when the contact pressure with the mating material is small.

（２）本開示の電気接点材料の一例として、
前記酸化物層中の各元素の原子濃度は、
酸素が０原子％超７０原子％以下、
亜鉛が０原子％超７０原子％以下、
銅が０原子％超３０原子％以下、
スズが０原子％超３０原子％以下、である形態が挙げられる。 (2) As an example of the electrical contact material of the present disclosure,
The atomic concentration of each element in the oxide layer is
Oxygen is more than 0 atomic% and 70 atomic% or less,
Zinc is more than 0 atomic% and 70 atomic% or less,
Copper is more than 0 atomic% and less than 30 atomic%,
Examples thereof include a form in which tin is more than 0 atomic% and 30 atomic% or less.

上記に列挙する原子濃度を満たす酸化物層は、導電率を向上し易い。そのため、上記に列挙する原子濃度を満たす酸化物層を備える電気接点材料は、金属層の表面に酸化物層が存在する状態であっても、相手材との間でより良好な電気的接続を確保できる。また、上記に列挙する原子濃度を満たす酸化物層を備える電気接点材料は、基材の酸化を抑制し易く、安定した耐久性を確保し易い。 An oxide layer satisfying the atomic concentrations listed above tends to improve the conductivity. Therefore, an electrical contact material provided with an oxide layer that satisfies the atomic concentrations listed above will have a better electrical connection with the mating material even when the oxide layer is present on the surface of the metal layer. Can be secured. Further, the electric contact material provided with the oxide layer satisfying the atomic concentrations listed above easily suppresses the oxidation of the base material and easily secures stable durability.

（３）本開示の電気接点材料の一例として、
前記酸化物層の平均厚さは、１ｎｍ以上１０００ｎｍ以下である形態が挙げられる。 (3) As an example of the electrical contact material of the present disclosure,
Examples thereof include a form in which the average thickness of the oxide layer is 1 nm or more and 1000 nm or less.

酸化物層の平均厚さが１ｎｍ以上であることで、基材の表面に被覆される被覆層（金属層と酸化物層とを合わせた層）の厚さを厚くでき、基材の酸化を抑制し易い。一方、酸化物層の平均厚さが１０００ｎｍ以下であることで、低抵抗の酸化物層とし易い。酸化物層が低抵抗であることで、本開示の電気接点材料は、金属層の表面に酸化物層が存在する状態であっても、相手材との間でより良好な電気的接続を確保できる。 When the average thickness of the oxide layer is 1 nm or more, the thickness of the coating layer (the layer in which the metal layer and the oxide layer are combined) coated on the surface of the base material can be increased, and the base material can be oxidized. Easy to suppress. On the other hand, when the average thickness of the oxide layer is 1000 nm or less, it is easy to form an oxide layer having low resistance. Due to the low resistance of the oxide layer, the electrical contact material of the present disclosure ensures better electrical connection with the mating material even in the presence of the oxide layer on the surface of the metal layer. it can.

（４）本開示の電気接点材料の一例として、
前記金属層は、
前記基材側に設けられる第一金属層と、
前記酸化物層側に設けられる第二金属層とを備え、
前記第一金属層は、亜鉛、銅、及びスズからなる群より選択される２種以上の元素を含む合金からなり、
前記第二金属層は、スズ又はスズ合金からなる形態が挙げられる。 (4) As an example of the electrical contact material of the present disclosure,
The metal layer is
The first metal layer provided on the base material side and
A second metal layer provided on the oxide layer side is provided.
The first metal layer is composed of an alloy containing two or more elements selected from the group consisting of zinc, copper, and tin.
The second metal layer may be in the form of tin or a tin alloy.

金属層における酸化物層側に第二金属層を備えることで、金属層に含まれる銅が酸化物層側に拡散することを抑制し易い。酸化物層側への銅の拡散を抑制できることで、酸化物層の直下における原子濃度比Ｃｕ／Ｓｎが１．４未満を満たし易い。そのため、酸化物層に銅の酸化物がより形成され難い。酸化物層に銅の酸化物がより少ないことで、本開示の電気接点材料は、金属層の表面に酸化物層が存在する状態であっても、相手材との間でより良好な電気的接続を確保できる。 By providing the second metal layer on the oxide layer side of the metal layer, it is easy to suppress the diffusion of copper contained in the metal layer to the oxide layer side. Since the diffusion of copper to the oxide layer side can be suppressed, the atomic concentration ratio Cu / Sn directly under the oxide layer can easily satisfy less than 1.4. Therefore, it is more difficult for copper oxide to be formed in the oxide layer. Due to the less copper oxide in the oxide layer, the electrical contact materials of the present disclosure have better electrical contact with the mating material, even in the presence of the oxide layer on the surface of the metal layer. You can secure a connection.

（５）金属層が第一金属層及び第二金属層を備える本開示の電気接点材料の一例として、
前記第一金属層の平均厚さは、０．１μｍ以上５μｍ以下である形態が挙げられる。 (5) As an example of the electrical contact material of the present disclosure in which the metal layer includes a first metal layer and a second metal layer,
The average thickness of the first metal layer may be 0.1 μm or more and 5 μm or less.

第一金属層の平均厚さが０．１μｍ以上であることで、基材の表面に被覆される被覆層（金属層と酸化物層とを合わせた層）の厚さを厚くでき、基材の酸化を抑制し易い。一方、第一金属層の平均厚さが５μｍ以下であることで、金属層の厚肉化を抑制できる。また、第一金属層の平均厚さが５μｍ以下であることで、金属層を形成する際の長時間化を抑制できる。 When the average thickness of the first metal layer is 0.1 μm or more, the thickness of the coating layer (layer in which the metal layer and the oxide layer are combined) coated on the surface of the base material can be increased, and the base material can be thickened. It is easy to suppress the oxidation of. On the other hand, when the average thickness of the first metal layer is 5 μm or less, it is possible to suppress the thickening of the metal layer. Further, when the average thickness of the first metal layer is 5 μm or less, it is possible to suppress a long time when forming the metal layer.

（６）金属層が第一金属層及び第二金属層を備える本開示の電気接点材料の一例として、
前記第二金属層の平均厚さは、０．１μｍ以上５μｍ以下である形態が挙げられる。 (6) As an example of the electrical contact material of the present disclosure in which the metal layer includes a first metal layer and a second metal layer,
The average thickness of the second metal layer may be 0.1 μm or more and 5 μm or less.

第二金属層の平均厚さが０．１μｍ以上であることで、基材の表面に被覆される被覆層（金属層と酸化物層とを合わせた層）の厚さを厚くでき、基材の酸化を抑制し易い。また、第二金属層の平均厚さが０．１μｍ以上であることで、金属層に含まれる銅が酸化物層側に拡散することをより抑制し易い。酸化物層側への銅の拡散を抑制できることで、酸化物層の直下における原子濃度比Ｃｕ／Ｓｎが１．４未満を満たし易い。そのため、酸化物層に銅の酸化物がより形成され難い。一方、第二金属層の平均厚さが５μｍ以下であることで、金属層の厚肉化を抑制できる。また、第二金属層の平均厚さが５μｍ以下であることで、金属層を形成する際の長時間化を抑制できる。 When the average thickness of the second metal layer is 0.1 μm or more, the thickness of the coating layer (layer in which the metal layer and the oxide layer are combined) coated on the surface of the base material can be increased, and the base material can be thickened. It is easy to suppress the oxidation of. Further, when the average thickness of the second metal layer is 0.1 μm or more, it is easier to suppress the diffusion of copper contained in the metal layer to the oxide layer side. Since the diffusion of copper to the oxide layer side can be suppressed, the atomic concentration ratio Cu / Sn directly under the oxide layer can easily satisfy less than 1.4. Therefore, it is more difficult for copper oxide to be formed in the oxide layer. On the other hand, when the average thickness of the second metal layer is 5 μm or less, it is possible to suppress the thickening of the metal layer. Further, when the average thickness of the second metal layer is 5 μm or less, it is possible to suppress the lengthening of time when forming the metal layer.

（７）本開示の実施形態に係る端子金具は、
上記（１）から（６）のいずれか１つに記載の電気接点材料からなる。 (7) The terminal fitting according to the embodiment of the present disclosure is
It is made of the electrical contact material according to any one of (1) to (6) above.

本開示の端子金具は、本開示の電気接点材料からなるため、相手材との接触圧力が小さい場合であっても、接触抵抗の上昇を抑制できる。 Since the terminal fitting of the present disclosure is made of the electrical contact material of the present disclosure, an increase in contact resistance can be suppressed even when the contact pressure with the mating material is small.

（８）本開示の実施形態に係るコネクタは、
上記（７）に記載の端子金具を備える。 (8) The connector according to the embodiment of the present disclosure is
The terminal fitting described in (7) above is provided.

本開示のコネクタは、本開示の端子金具を備えるため、相手材との接触圧力が小さい場合であっても、接触抵抗の上昇を抑制できる。 Since the connector of the present disclosure includes the terminal fitting of the present disclosure, it is possible to suppress an increase in contact resistance even when the contact pressure with the mating material is small.

（９）本開示の実施形態に係るワイヤーハーネスは、
電線と、
前記電線に取り付けられる上記（７）に記載の端子金具、又は上記（８）に記載のコネクタとを備える。 (9) The wire harness according to the embodiment of the present disclosure is
With electric wires
It is provided with the terminal fitting according to the above (7) or the connector according to the above (8) attached to the electric wire.

本開示のワイヤーハーネスは、本開示の端子金具又は本開示のコネクタを備えるため、相手材との接触圧力が小さい場合であっても、接触抵抗の上昇を抑制できる。 Since the wire harness of the present disclosure includes the terminal fitting of the present disclosure or the connector of the present disclosure, it is possible to suppress an increase in contact resistance even when the contact pressure with the mating material is small.

（１０）本開示の実施形態に係る電気接点材料の製造方法は、
基材の表面の少なくとも一部に、前記基材側から順に、第一層、第二層、及び第三層をめっきにより被覆した被覆材料を作製する工程と、
前記被覆材料に、酸素雰囲気中、２３２℃以上５００℃以下の温度で熱処理を施す工程とを備え、
前記被覆材料を作製する工程では、
前記第一層は、スズを含む金属からなり、
前記第二層は、亜鉛を含む金属からなり、
前記第三層は、銅を含む金属からなり、
前記第一層の厚さを３．５μｍ以上５μｍ以下、
前記第二層の厚さを０．１μｍ以上０．６μｍ以下、
前記第三層の厚さを０．０５μｍ以上０．４μｍ以下とする。 (10) The method for manufacturing an electrical contact material according to the embodiment of the present disclosure is as follows.
A step of producing a coating material in which the first layer, the second layer, and the third layer are coated by plating on at least a part of the surface of the base material in order from the base material side.
The coating material is provided with a step of heat-treating the coating material at a temperature of 232 ° C. or higher and 500 ° C. or lower in an oxygen atmosphere.
In the step of producing the coating material,
The first layer is made of a metal containing tin and
The second layer is made of a metal containing zinc and
The third layer is made of a metal containing copper.
The thickness of the first layer is 3.5 μm or more and 5 μm or less.
The thickness of the second layer is 0.1 μm or more and 0.6 μm or less.
The thickness of the third layer is 0.05 μm or more and 0.4 μm or less.

本開示の電気接点材料の製造方法は、基材側から順に、スズを含む第一層、亜鉛を含む第二層、及び銅を含む第三層をめっきにより被覆する。第一層、第二層、及び第三層からなる被覆層が被覆された被覆材料は、経時的に合金化反応を起こす。一方で、上記被覆材料に熱処理を施すことで、被覆材料の表面に酸化物層が形成される。このとき、被覆層における各層の厚さが上記範囲を満たすことで、酸化物層側にスズが拡散され易く、銅が拡散され難い。具体的には、２３２℃以上の温度で熱処理を行うことで、スズを液相状態とでき、上記範囲の厚さを有する第一層中のスズが上記酸化物層側に拡散され易い。また、２３２℃以上の温度で熱処理を行うことで、酸化物層中にスズや亜鉛を含有させ易く、銅を含有させ難い。一方、５００℃以下の温度で熱処理を行うことで、上記範囲の厚さを有する第三層中の銅が上記酸化物層側に拡散され難い。以上より、本開示の電気接点材料の製造方法によれば、基材の表面にスズ、亜鉛、及び銅を含む合金からなる金属層を形成できると共に、その金属層の表面にスズ、亜鉛、及び銅を含む酸化物からなる酸化物層を形成できる。このとき、被覆層における各層の厚さが上記範囲を満たすと共に、上記範囲の温度で熱処理を施すことで、スズと銅の拡散が制御され、酸化物層直下における原子濃度比Ｃｕ／Ｓｎを１．４未満とできる。 In the method for producing an electrical contact material of the present disclosure, the first layer containing tin, the second layer containing zinc, and the third layer containing copper are coated by plating in order from the base material side. The coating material coated with the coating layer composed of the first layer, the second layer, and the third layer undergoes an alloying reaction over time. On the other hand, by heat-treating the coating material, an oxide layer is formed on the surface of the coating material. At this time, when the thickness of each layer in the coating layer satisfies the above range, tin is easily diffused to the oxide layer side, and copper is hard to be diffused. Specifically, by performing the heat treatment at a temperature of 232 ° C. or higher, tin can be put into a liquid phase state, and tin in the first layer having a thickness in the above range is easily diffused to the oxide layer side. Further, by performing the heat treatment at a temperature of 232 ° C. or higher, tin and zinc are likely to be contained in the oxide layer, and copper is difficult to be contained. On the other hand, by performing the heat treatment at a temperature of 500 ° C. or lower, copper in the third layer having a thickness in the above range is unlikely to be diffused to the oxide layer side. Based on the above, according to the method for producing an electrical contact material of the present disclosure, a metal layer made of an alloy containing tin, zinc, and copper can be formed on the surface of a base material, and tin, zinc, and tin, zinc, and copper can be formed on the surface of the metal layer. An oxide layer made of an oxide containing copper can be formed. At this time, the thickness of each layer in the coating layer satisfies the above range, and the diffusion of tin and copper is controlled by performing the heat treatment at the temperature in the above range, and the atomic concentration ratio Cu / Sn directly under the oxide layer is set to 1. Can be less than 0.4.

［本開示の実施形態の詳細］
本開示の実施形態の詳細を、以下に説明する。なお、本発明はこれらの例示に限定されるものではなく、特許請求の範囲によって示され、特許請求の範囲と均等の意味及び範囲内でのすべての変更が含まれることが意図される。 [Details of Embodiments of the present disclosure]
Details of the embodiments of the present disclosure will be described below. It should be noted that the present invention is not limited to these examples, and is indicated by the scope of claims, and is intended to include all modifications within the meaning and scope equivalent to the scope of claims.

≪電気接点材料≫
実施形態に係る電気接点材料１は、図１に示すように、金属からなる基材１０と、基材１０の表面に設けられる金属層２０と、金属層２０の表面に設けられる酸化物層３０とを備える。金属層２０は、亜鉛（Ｚｎ）、銅（Ｃｕ）、及びスズ（Ｓｎ）を含む金属からなる。酸化物層３０は、Ｚｎ、Ｃｕ、及びＳｎを含む酸化物からなる。実施形態に係る電気接点材料１は、酸化物層３０の直下において、Ｓｎの原子濃度に対するＣｕの原子濃度の比率（以下、原子濃度比Ｃｕ／Ｓｎと呼ぶことがある）が１．４未満である点を特徴の一つとする。 ≪Electrical contact material≫
As shown in FIG. 1, the electrical contact material 1 according to the embodiment includes a base material 10 made of metal, a metal layer 20 provided on the surface of the base material 10, and an oxide layer 30 provided on the surface of the metal layer 20. And. The metal layer 20 is made of a metal containing zinc (Zn), copper (Cu), and tin (Sn). The oxide layer 30 is made of an oxide containing Zn, Cu, and Sn. In the electrical contact material 1 according to the embodiment, the ratio of the atomic concentration of Cu to the atomic concentration of Sn (hereinafter, may be referred to as the atomic concentration ratio Cu / Sn) is less than 1.4 immediately under the oxide layer 30. One of the features is a certain point.

〔基材〕
基材１０は、金属からなる。特に、基材１０は、導電性に優れるＣｕ、Ｃｕ合金、アルミニウム（Ａｌ）、Ａｌ合金、鉄（Ｆｅ）、及びＦｅ合金から選択される一種以上の金属からなることが好適である。基材１０の形状は、棒状や板状などの種々の形状を適宜選択できる。また、基材１０の寸法は、用途に応じて種々の寸法を適宜選択できる。 〔Base material〕
The base material 10 is made of metal. In particular, the base material 10 is preferably made of one or more metals selected from Cu, Cu alloy, aluminum (Al), Al alloy, iron (Fe), and Fe alloy having excellent conductivity. As the shape of the base material 10, various shapes such as a rod shape and a plate shape can be appropriately selected. In addition, various dimensions of the base material 10 can be appropriately selected depending on the intended use.

基材１０の表面には、めっき層（図示せず）を備えてもよい。めっき層は、例えば、Ｃｕ、Ｃｕ合金、ニッケル（Ｎｉ）、Ｎｉ合金、コバルト（Ｃｏ）、及びＣｏ合金からなる群より選択される１種以上の金属を含むことが挙げられる。基材１０の表面にめっき層を備えることで、基材１０の表面に設けられる金属層２０との密着性を向上できる。また、基材１０とめっき層とが同種金属の場合、基材１０の構成元素が金属層２０側に拡散することを促進できる。例えば、Ｃｕを含む金属板の表面にＣｕを含むめっき層を備える場合、基材１０中のＣｕが金属層２０側に拡散することを促進できる。めっき層の厚さは、０．０１μｍ以上５μｍ以下が挙げられ、更に０．１μｍ以上３μｍ以下が挙げられる。ここでのめっき層の厚さは、電気接点材料１の製造過程において、基材１０の表面にめっきしたときの厚さである。 A plating layer (not shown) may be provided on the surface of the base material 10. The plating layer may contain, for example, one or more metals selected from the group consisting of Cu, Cu alloys, nickel (Ni), Ni alloys, cobalt (Co), and Co alloys. By providing the plating layer on the surface of the base material 10, the adhesion to the metal layer 20 provided on the surface of the base material 10 can be improved. Further, when the base material 10 and the plating layer are the same type of metal, it is possible to promote the diffusion of the constituent elements of the base material 10 toward the metal layer 20 side. For example, when a plating layer containing Cu is provided on the surface of a metal plate containing Cu, it is possible to promote the diffusion of Cu in the base material 10 toward the metal layer 20 side. The thickness of the plating layer is 0.01 μm or more and 5 μm or less, and further, 0.1 μm or more and 3 μm or less. The thickness of the plating layer here is the thickness when the surface of the base material 10 is plated in the manufacturing process of the electrical contact material 1.

〔金属層〕
金属層２０は、基材１０の酸化を抑制する機能を有する。金属層２０は、基材１０とは組成が異なる。金属層２０は、基材１０よりも酸化し難い組成からなることが好ましい。この例では、金属層２０は、第一金属層２１と第二金属層２２とを備える多層構造となっている。 [Metal layer]
The metal layer 20 has a function of suppressing oxidation of the base material 10. The composition of the metal layer 20 is different from that of the base material 10. The metal layer 20 preferably has a composition that is less likely to be oxidized than the base material 10. In this example, the metal layer 20 has a multi-layer structure including a first metal layer 21 and a second metal layer 22.

（第一金属層）
第一金属層２１は、金属層２０における基材１０側に設けられる。第一金属層２１は、Ｚｎ、Ｃｕ、及びＳｎからなる群より選択される２種以上の元素を含む合金からなる。第一金属層２１中の各元素の原子濃度は、Ｚｎが０．０１原子％以上５０原子％以下、Ｃｕが１０原子％以上９０原子％以下、Ｓｎが１０原子％以上９０原子％以下であることが挙げられる。上記に列挙する原子濃度を満たすことで、第一金属層２１は、例えば、（Ｃｕ，Ｚｎ）６Ｓｎ５で示される金属間化合物を含有する。第一金属層２１中の各元素の原子濃度は、更にＺｎが０．１原子％以上３０原子％以下、Ｃｕが４０原子％以上８０原子％以下、Ｓｎが２０原子％以上５０原子％以下であることが挙げられる。第一金属層２１中の各元素の原子濃度は、例えば、蛍光Ｘ線分析装置を用いて測定できる。第一金属層２１は、主に、電気接点材料１の製造過程において、基材１０の表面に金属層２０の構成材料をめっきした後に経時的に生じる合金化反応によって形成される。つまり、この第一金属層２１は、主に、電気接点材料１の製造過程において、基材１０の表面に金属層２０の構成材料をめっきした後の放置時及び熱処理時に形成される。 (First metal layer)
The first metal layer 21 is provided on the base material 10 side of the metal layer 20. The first metal layer 21 is made of an alloy containing two or more elements selected from the group consisting of Zn, Cu, and Sn. The atomic concentration of each element in the first metal layer 21 is 0.01 atomic% or more and 50 atomic% or less for Zn, 10 atomic% or more and 90 atomic% or less for Cu, and 10 atomic% or more and 90 atomic% or less for Sn. Can be mentioned. By satisfying the atomic concentrations listed above, the first metal layer 21 contains, for example, an intermetallic compound represented by (Cu, Zn) 6 Sn 5 . The atomic concentration of each element in the first metal layer 21 is 0.1 atomic% or more and 30 atomic% or less for Zn, 40 atomic% or more and 80 atomic% or less for Cu, and 20 atomic% or more and 50 atomic% or less for Sn. There is one thing. The atomic concentration of each element in the first metal layer 21 can be measured using, for example, a fluorescent X-ray analyzer. The first metal layer 21 is mainly formed by an alloying reaction that occurs over time after plating the constituent material of the metal layer 20 on the surface of the base material 10 in the manufacturing process of the electrical contact material 1. That is, the first metal layer 21 is mainly formed in the manufacturing process of the electrical contact material 1 when the constituent material of the metal layer 20 is plated on the surface of the base material 10 and then left to stand and when heat-treated.

第一金属層２１は、平均厚さが０．１μｍ以上５μｍ以下であることが挙げられる。第一金属層２１の平均厚さが０．１μｍ以上であることで、基材１０の表面に被覆される被覆層（金属層２０と酸化物層３０とを合わせた層）の厚さを厚くでき、基材１０の酸化を抑制し易い。一方、第一金属層２１の平均厚さが５μｍ以下であることで、金属層２０の厚肉化を抑制できる。また、第一金属層２１の平均厚さが５μｍ以下であることで、金属層２０を形成する際の長時間化を抑制できる。第一金属層２１の平均厚さは、更に０．５μｍ以上４．５μｍ以下、特に１．０μｍ以上４．０μｍ以下、２．０μｍ以上４．０μｍ以下が挙げられる。第一金属層２１の平均厚さは、例えば、蛍光Ｘ線膜厚計を用いて以下のように測定できる。第一金属層２１よりも上層の酸化物層３０及び第二金属層２２を除去する。その後、第一金属層２１における特定面積中のＳｎの含有量を蛍光Ｘ線膜厚計により測定し、第一金属層２１の組成及び密度から第一金属層２１の厚さを演算する。第一金属層２１における上記特定面積を例えば１０箇所選択し、各特定面積について演算して得られた第一金属層２１の厚さの平均値を算出し、その平均値を第一金属層２１の平均厚さとする。 The first metal layer 21 has an average thickness of 0.1 μm or more and 5 μm or less. When the average thickness of the first metal layer 21 is 0.1 μm or more, the thickness of the coating layer (a layer obtained by combining the metal layer 20 and the oxide layer 30) coated on the surface of the base material 10 is increased. It is possible to easily suppress the oxidation of the base material 10. On the other hand, when the average thickness of the first metal layer 21 is 5 μm or less, it is possible to suppress the thickening of the metal layer 20. Further, when the average thickness of the first metal layer 21 is 5 μm or less, it is possible to suppress the lengthening of time when forming the metal layer 20. Further, the average thickness of the first metal layer 21 is 0.5 μm or more and 4.5 μm or less, particularly 1.0 μm or more and 4.0 μm or less, and 2.0 μm or more and 4.0 μm or less. The average thickness of the first metal layer 21 can be measured as follows, for example, using a fluorescent X-ray film thickness meter. The oxide layer 30 and the second metal layer 22 above the first metal layer 21 are removed. Then, the Sn content in the specific area of the first metal layer 21 is measured by a fluorescent X-ray film thickness meter, and the thickness of the first metal layer 21 is calculated from the composition and density of the first metal layer 21. For example, 10 specific areas of the first metal layer 21 are selected, an average value of the thicknesses of the first metal layer 21 obtained by calculating for each specific area is calculated, and the average value is used as the average value of the first metal layer 21. The average thickness of.

（第二金属層）
第二金属層２２は、金属層２０における酸化物層３０側に設けられる。第二金属層２２は、Ｓｎ又はＳｎ合金からなる。第二金属層２２は、第一金属層２１と酸化物層３０との間に介在される。第二金属層２２は、第一金属層２１に比較して、Ｃｕの原子濃度がＳｎの原子濃度よりも十分に小さい層である。第二金属層２２がＳｎ合金からなり、Ｓｎ以外の添加元素としてＣｕを含む場合、Ｃｕの原子濃度は、０．０１原子％以上５０原子％以下が挙げられ、更に０．１原子％以上３０原子％以下が挙げられる。また、第二金属層２２がＳｎ合金からなり、Ｓｎ以外の添加元素としてＺｎを含む場合、Ｚｎの原子濃度は、０．０１原子％以上５０原子％以下が挙げられ、更に０．１原子％以上４０原子％以下が挙げられる。第二金属層２２中の各元素の原子濃度は、例えば、蛍光Ｘ線分析装置を用いて測定できる。第二金属層２２は、主に、電気接点材料１の製造過程において、基材１０の表面に設けられたＳｎが液相状態となることで形成される。つまり、第二金属層２２は、主に、電気接点材料１の製造過程において、基材１０の表面に金属層２０の構成材料をめっきした後の熱処理時に形成される。 (Second metal layer)
The second metal layer 22 is provided on the oxide layer 30 side of the metal layer 20. The second metal layer 22 is made of Sn or a Sn alloy. The second metal layer 22 is interposed between the first metal layer 21 and the oxide layer 30. The second metal layer 22 is a layer in which the atomic concentration of Cu is sufficiently smaller than the atomic concentration of Sn as compared with the first metal layer 21. When the second metal layer 22 is made of a Sn alloy and contains Cu as an additive element other than Sn, the atomic concentration of Cu is 0.01 atomic% or more and 50 atomic% or less, and further 0.1 atomic% or more and 30. Atomic% or less can be mentioned. When the second metal layer 22 is made of a Sn alloy and contains Zn as an additive element other than Sn, the atomic concentration of Zn is 0.01 atomic% or more and 50 atomic% or less, and further 0.1 atomic%. More than 40 atomic% or less. The atomic concentration of each element in the second metal layer 22 can be measured using, for example, a fluorescent X-ray analyzer. The second metal layer 22 is mainly formed by bringing Sn provided on the surface of the base material 10 into a liquid phase state in the manufacturing process of the electrical contact material 1. That is, the second metal layer 22 is mainly formed during the heat treatment after plating the constituent material of the metal layer 20 on the surface of the base material 10 in the manufacturing process of the electrical contact material 1.

第二金属層２２は、平均厚さが０．１μｍ以上５μｍ以下であることが挙げられる。第二金属層２２の平均厚さが０．１μｍ以上であることで、基材１０の表面に被覆される被覆層（金属層２０と酸化物層３０とを合わせた層）の厚さを厚くでき、基材１０の酸化を抑制し易い。また、第二金属層２２の平均厚さが０．１μｍ以上であることで、第一金属層２１に含まれるＣｕが酸化物層３０側に拡散することを抑制し易い。更に、第二金属層２２の平均厚さが０．１μｍ以上であることで、基材１０にＣｕを含む場合には、基材１０に含まれるＣｕが酸化物層３０側に拡散することも抑制し易い。酸化物層３０側へのＣｕの拡散を抑制できることで、酸化物層３０の直下における原子濃度比Ｃｕ／Ｓｎが１．４未満を満たし易い。一方、第二金属層２２の平均厚さが５μｍ以下であることで、金属層２０の厚肉化を抑制できる。また、第二金属層２２の平均厚さが５μｍ以下であることで、金属層２０を形成する際の長時間化を抑制できる。第二金属層２２の平均厚さは、更に０．２μｍ以上４．０μｍ以下、特に０．３μｍ以上３．０μｍ以下、０．３μｍ以上１．０μｍ以下が挙げられる。第二金属層２２の平均厚さは、例えば、蛍光Ｘ線膜厚計を用いて以下のように測定できる。金属層２０全体における特定面積中のＳｎの含有量を蛍光Ｘ線膜厚計により測定する。その後、第二金属層２２のみを溶解できる処理液を用いて、エッチングにより第二金属層２２のみを除去する。残存した第一金属層２１における上記特定面積中のＳｎの含有量を蛍光Ｘ線膜厚計により測定する。第二金属層２２の厚さは、測定した金属層２０全体における特定面積中のＳｎの含有量と、第一金属層２１における同特定面積中のＳｎの含有量との差から演算できる。上記特定面積を例えば１０箇所選択し、各特定面積について演算して得られた第二金属層２２の厚さの平均値を算出し、その平均値を第二金属層２２の平均厚さとする。 The second metal layer 22 has an average thickness of 0.1 μm or more and 5 μm or less. When the average thickness of the second metal layer 22 is 0.1 μm or more, the thickness of the coating layer (a layer obtained by combining the metal layer 20 and the oxide layer 30) coated on the surface of the base material 10 is increased. It is possible to easily suppress the oxidation of the base material 10. Further, when the average thickness of the second metal layer 22 is 0.1 μm or more, it is easy to prevent Cu contained in the first metal layer 21 from diffusing toward the oxide layer 30 side. Further, since the average thickness of the second metal layer 22 is 0.1 μm or more, when the base material 10 contains Cu, the Cu contained in the base material 10 may diffuse to the oxide layer 30 side. Easy to suppress. Since the diffusion of Cu to the oxide layer 30 side can be suppressed, the atomic concentration ratio Cu / Sn immediately below the oxide layer 30 can easily be satisfied to be less than 1.4. On the other hand, when the average thickness of the second metal layer 22 is 5 μm or less, it is possible to suppress the thickening of the metal layer 20. Further, when the average thickness of the second metal layer 22 is 5 μm or less, it is possible to suppress a long time when forming the metal layer 20. Further, the average thickness of the second metal layer 22 is 0.2 μm or more and 4.0 μm or less, particularly 0.3 μm or more and 3.0 μm or less, and 0.3 μm or more and 1.0 μm or less. The average thickness of the second metal layer 22 can be measured, for example, using a fluorescent X-ray film thickness meter as follows. The Sn content in a specific area in the entire metal layer 20 is measured by a fluorescent X-ray film thickness meter. Then, only the second metal layer 22 is removed by etching using a treatment liquid capable of dissolving only the second metal layer 22. The Sn content in the specific area of the remaining first metal layer 21 is measured by a fluorescent X-ray film thickness meter. The thickness of the second metal layer 22 can be calculated from the difference between the measured Sn content in the specific area of the entire metal layer 20 and the Sn content in the specific area of the first metal layer 21. For example, 10 specific areas are selected, the average value of the thickness of the second metal layer 22 obtained by calculating for each specific area is calculated, and the average value is taken as the average thickness of the second metal layer 22.

〔酸化物層〕
酸化物層３０は、金属層２０の表面に設けられる。酸化物層３０は、主に、電気接点材料１の製造過程において、金属層２０の構成元素が酸化されて形成される。酸化物層３０は、電気接点材料１の最表面を構成する。 [Oxide layer]
The oxide layer 30 is provided on the surface of the metal layer 20. The oxide layer 30 is mainly formed by oxidizing the constituent elements of the metal layer 20 in the manufacturing process of the electrical contact material 1. The oxide layer 30 constitutes the outermost surface of the electrical contact material 1.

酸化物層３０は、例えば、ＺｎＯ、ＳｎＯ、ＳｎＯ２、ＣｕＯ、ＣｕＯ２などの酸化物が混合して存在し得る。また、酸化物層３０は、上記各種酸化物からなる化合物として存在し得る。ＺｎＯは、Ｚｎの一部がＣｕやＳｎに置換して、（Ｚｎ，Ｃｕ）Ｏや（Ｚｎ，Ｓｎ）Ｏの形態で存在し得る。酸化物層３０は、後述するようにＣｕの酸化物が他の酸化物に比較して少ない。具体的には、酸化物層３０は、Ｃｕの酸化物がＺｎの酸化物に比較して少ない。Ｃｕの酸化物が少ない酸化物層３０は、導電性を確保し易い。 The oxide layer 30 may contain a mixture of oxides such as ZnO, SnO, SnO 2 , CuO, and CuO 2 . Further, the oxide layer 30 may exist as a compound composed of the above-mentioned various oxides. ZnO may exist in the form of (Zn, Cu) O or (Zn, Sn) O by substituting a part of Zn with Cu or Sn. As will be described later, the oxide layer 30 contains less Cu oxide than other oxides. Specifically, the oxide layer 30 contains less Cu oxide than Zn oxide. The oxide layer 30 having a small amount of Cu oxide can easily secure conductivity.

酸化物層３０中の各元素の原子濃度は、Ｏが０原子％超７０原子％以下、Ｚｎが０原子％超７０原子％以下、Ｃｕが０原子％超３０原子％以下、Ｓｎが０原子％超３０原子％以下であることが挙げられる。上記に列挙する原子濃度を満たすことで、酸化物層３０は、導電率を向上し易い。また、上記に列挙する原子濃度を満たすことで、基材１０の酸化を抑制し易い。酸化物層３０中の各元素の原子濃度は、更にＯが１０原子％以上６０原子％以下、Ｚｎが１０原子％以上６０原子％以下、Ｃｕが０．１原子％以上２０原子％以下、Ｓｎが０．１原子％以上２０原子％以下であることが挙げられる。酸化物層３０中の各元素の原子濃度は、特にＯが４０原子％以上５５原子％以下、Ｚｎが３５原子％以上６０原子％以下、Ｃｕが５原子％以上１５原子％以下、Ｓｎが０．１原子％以上１０原子％以下であることが挙げられる。酸化物層３０中の各元素の原子濃度は、例えば、Ｘ線光電子分光分析を用いて測定できる。酸化物層３０は、主に、電気接点材料１の製造過程において、基材１０の表面に設けられた金属層２０の構成元素が酸化されて形成される。つまり、酸化物層３０は、主に、電気接点材料１の製造過程において、基材１０の表面に金属層２０の構成材料をめっきした後の熱処理時に形成される。 The atomic concentration of each element in the oxide layer 30 is as follows: O is more than 0 atomic% and 70 atomic% or less, Zn is more than 0 atomic% and 70 atomic% or less, Cu is more than 0 atomic% and 30 atomic% or less, and Sn is 0 atom. It is mentioned that it is more than% and less than 30 atomic%. By satisfying the atomic concentrations listed above, the oxide layer 30 can easily improve the conductivity. Further, by satisfying the atomic concentrations listed above, it is easy to suppress the oxidation of the base material 10. The atomic concentration of each element in the oxide layer 30 is as follows: O is 10 atomic% or more and 60 atomic% or less, Zn is 10 atomic% or more and 60 atomic% or less, Cu is 0.1 atomic% or more and 20 atomic% or less, Sn. Is 0.1 atomic% or more and 20 atomic% or less. The atomic concentration of each element in the oxide layer 30 is as follows: O is 40 atomic% or more and 55 atomic% or less, Zn is 35 atomic% or more and 60 atomic% or less, Cu is 5 atomic% or more and 15 atomic% or less, and Sn is 0. . 1 atomic% or more and 10 atomic% or less. The atomic concentration of each element in the oxide layer 30 can be measured using, for example, X-ray photoelectron spectroscopy. The oxide layer 30 is mainly formed by oxidizing the constituent elements of the metal layer 20 provided on the surface of the base material 10 in the manufacturing process of the electrical contact material 1. That is, the oxide layer 30 is mainly formed during the heat treatment after plating the constituent material of the metal layer 20 on the surface of the base material 10 in the manufacturing process of the electrical contact material 1.

酸化物層３０は、平均厚さが１ｎｍ以上１０００ｎｍ以下であることが挙げられる。酸化物層３０の平均厚さが１ｎｍ以上であることで、基材１０の表面に被覆される被覆層（金属層２０と酸化物層３０とを合わせた層）の厚さを厚くでき、基材１０の酸化を抑制し易い。一方、酸化物層３０の平均厚さが１０００ｎｍ以下であることで、低抵抗の酸化物層３０とし易い。酸化物層３０の平均厚さは、更に３ｎｍ以上５００ｎｍ以下、特に１０ｎｍ以上３００ｎｍ以下、１５ｎｍ以上１００ｎｍ以下、２０ｎｍ以上８０ｎｍ以下が挙げられる。酸化物層３０の平均厚さは、例えば、任意の測定点を例えば１０箇所選択し、Ｘ線光電子分光分析を用いて、各測定点の厚さを測定し、それらの平均値を算出することで求められる。 The oxide layer 30 has an average thickness of 1 nm or more and 1000 nm or less. When the average thickness of the oxide layer 30 is 1 nm or more, the thickness of the coating layer (the layer in which the metal layer 20 and the oxide layer 30 are combined) coated on the surface of the base material 10 can be increased, and the base can be increased. It is easy to suppress the oxidation of the material 10. On the other hand, when the average thickness of the oxide layer 30 is 1000 nm or less, the oxide layer 30 having low resistance can be easily formed. Further, the average thickness of the oxide layer 30 is 3 nm or more and 500 nm or less, particularly 10 nm or more and 300 nm or less, 15 nm or more and 100 nm or less, and 20 nm or more and 80 nm or less. For the average thickness of the oxide layer 30, for example, 10 arbitrary measurement points are selected, the thickness of each measurement point is measured by using X-ray photoelectron spectroscopy, and the average value thereof is calculated. Is required by.

〔酸化物層の直下〕
酸化物層３０の直下は、Ｓｎの原子濃度に対するＣｕの原子濃度の比率（原子濃度比Ｃｕ／Ｓｎ）が１．４未満である。原子濃度比Ｃｕ／Ｓｎが１．４未満を満たすことで、酸化物層３０の直下に存在するＣｕは、主にＣｕ６Ｓｎ５の形態で存在し得る。ＣｕがＣｕ６Ｓｎ５の形態で存在することで、酸化物層３０にＣｕの酸化物が形成され難い。Ｃｕの酸化物が少ない酸化物層３０は、導電性を確保し易い。そのため、電気接点材料１は、最表面に酸化物層３０が存在する状態であっても、導電性の酸化物層３０及び金属層２０を介して、基材１０と相手材との間で良好な電気的接続を確保できる。なお、上記原子濃度比Ｃｕ／Ｓｎが１．４以上を満たす場合、酸化物層３０の直下に存在するＣｕは、主にＣｕ３Ｓｎの形態で存在し得る。ＣｕがＣｕ３Ｓｎの形態で存在すると、酸化物層３０にＣｕの酸化物が形成され易い。 [Directly below the oxide layer]
Immediately below the oxide layer 30, the ratio of the atomic concentration of Cu to the atomic concentration of Sn (atomic concentration ratio Cu / Sn) is less than 1.4. When the atomic concentration ratio Cu / Sn satisfies less than 1.4, the Cu existing immediately below the oxide layer 30 can exist mainly in the form of Cu 6 Sn 5 . Since Cu exists in the form of Cu 6 Sn 5 , it is difficult for an oxide of Cu to be formed in the oxide layer 30. The oxide layer 30 having a small amount of Cu oxide can easily secure conductivity. Therefore, the electrical contact material 1 is good between the base material 10 and the mating material via the conductive oxide layer 30 and the metal layer 20 even when the oxide layer 30 is present on the outermost surface. Can secure a good electrical connection. When the atomic concentration ratio Cu / Sn satisfies 1.4 or more, Cu existing immediately below the oxide layer 30 may mainly exist in the form of Cu 3 Sn. When Cu is present in the form of Cu 3 Sn, an oxide of Cu is likely to be formed in the oxide layer 30.

酸化物層３０の直下における原子濃度比Ｃｕ／Ｓｎは、小さいほど酸化物層３０にＣｕの酸化物が形成され難い。よって、酸化物層３０の直下における原子濃度比Ｃｕ／Ｓｎは、更に１．３以下が挙げられ、特に１．２以下が挙げられる。ここで言う酸化物層３０の直下とは、酸化物層３０と第二金属層２２との界面からの第二金属層２２側のＳｉＯ２のスパッタリングレート換算で０．０５μｍ以下の範囲を言う。上記原子濃度比Ｃｕ／Ｓｎは、Ｘ線光電子分光分析を用いて測定できる。 The smaller the atomic concentration ratio Cu / Sn immediately below the oxide layer 30, the more difficult it is for Cu oxide to be formed in the oxide layer 30. Therefore, the atomic concentration ratio Cu / Sn immediately below the oxide layer 30 is further preferably 1.3 or less, and particularly 1.2 or less. The term "directly below the oxide layer 30" as used herein means a range of 0.05 μm or less in terms of the sputtering rate of SiO 2 on the second metal layer 22 side from the interface between the oxide layer 30 and the second metal layer 22. The atomic concentration ratio Cu / Sn can be measured by using X-ray photoelectron spectroscopy.

≪端子金具、コネクタ、及びワイヤーハーネス≫
上記電気接点材料１は、端子金具、コネクタ、及びワイヤーハーネスに好適に利用することができる。図３にメス型の端子金具２００を示す。この端子金具２００は、電線３００に備わる導体３１０を接続する導体接続部として、一対の圧着片を主体とするワイヤバレル部２１０を備える圧着タイプである。端子金具２００は、更に電線３００の絶縁層３２０を圧着するインシュレーションバレル部２２０も備える。端子金具２００は、ワイヤバレル部２１０の一方の側にメス型の嵌合部２３０を備える。嵌合部２３０は、筒状の箱部２３１と、箱部２３１の内面に対向配置された弾性片２３２，２３３とを備える。この弾性片２３２，２３３の少なくとも一方が、上記電気接点材料１からなる。メス型の嵌合部２３０の箱部２３１にオス型の嵌合部（図示せず）が挿入されることで、オス型の嵌合部がメス型の嵌合部２３０の弾性片２３２，２３３の付勢力によって強固に挟持され、メス型の端子金具２００とオス型の端子金具とが電気的に接続される。上記電気接点材料１は、相手材との接触圧力が小さい場合であっても、接触抵抗の増加を抑制できることから、上記弾性片２３２，２３３が小さいような端子金具に好適に利用できる。 ≪Terminal fittings, connectors, and wire harness≫
The electrical contact material 1 can be suitably used for terminal fittings, connectors, and wire harnesses. FIG. 3 shows a female terminal fitting 200. The terminal fitting 200 is a crimping type including a wire barrel portion 210 mainly composed of a pair of crimping pieces as a conductor connecting portion for connecting the conductor 310 provided in the electric wire 300. The terminal fitting 200 also includes an insulation barrel portion 220 for crimping the insulating layer 320 of the electric wire 300. The terminal fitting 200 includes a female fitting portion 230 on one side of the wire barrel portion 210. The fitting portion 230 includes a tubular box portion 231 and elastic pieces 232 and 233 arranged to face each other on the inner surface of the box portion 231. At least one of the elastic pieces 232 and 233 is made of the electrical contact material 1. By inserting the male fitting portion (not shown) into the box portion 231 of the female fitting portion 230, the male fitting portion becomes the elastic piece 232,233 of the female fitting portion 230. It is firmly sandwiched by the urging force of the female terminal fitting 200 and the male terminal fitting 200 is electrically connected. Since the electrical contact material 1 can suppress an increase in contact resistance even when the contact pressure with the mating material is small, it can be suitably used for terminal fittings in which the elastic pieces 232 and 233 are small.

≪電気接点材料の製造方法≫
実施形態に係る電気接点材料の製造方法は、めっき工程と熱処理工程とを備える。 ≪Manufacturing method of electrical contact material≫
The method for producing an electrical contact material according to an embodiment includes a plating step and a heat treatment step.

〔めっき工程〕
めっき工程では、図２に示すように、基材１１０の表面の少なくとも一部に被覆層１２０をめっきにより被覆した被覆材料１００を作製する。基材１１０は、上述した電気接点材料１における基材１０である。被覆層１２０は、基材１１０側から順に、Ｓｎを含む金属からなる第一層１２１、Ｚｎを含む金属からなる第二層１２２、及びＣｕを含む金属からなる第三層１２３が積層された多層構造である。めっき方法としては、電気めっき、無電解めっき、溶融めっきなどが挙げられる。 [Plating process]
In the plating step, as shown in FIG. 2, a coating material 100 is produced in which at least a part of the surface of the base material 110 is coated with the coating layer 120 by plating. The base material 110 is the base material 10 in the above-mentioned electrical contact material 1. The coating layer 120 is a multilayer in which a first layer 121 made of a metal containing Sn, a second layer 122 made of a metal containing Zn, and a third layer 123 made of a metal containing Cu are laminated in this order from the base material 110 side. It is a structure. Examples of the plating method include electroplating, electroless plating, hot dip plating and the like.

（第一層）
第一層１２１は、後述する熱処理により第一金属層２１及び第二金属層２２を形成し、得られる電気接点材料１における表層（酸化物層３０）側へのＣｕの拡散を抑制するために設けられる。第一層１２１は、Ｓｎ又はＳｎ合金からなる。第一層１２１がＳｎ合金からなる場合、Ｓｎ以外の添加元素としてＣｕやＺｎを含むことが挙げられる。添加元素の原子濃度としては、０．１原子％以上５０原子％以下が挙げられ、更に１原子％以上３０原子％以下が挙げられる。 (First layer)
The first layer 121 forms the first metal layer 21 and the second metal layer 22 by the heat treatment described later, and in order to suppress the diffusion of Cu to the surface layer (oxide layer 30) side in the obtained electrical contact material 1. Provided. The first layer 121 is made of Sn or a Sn alloy. When the first layer 121 is made of a Sn alloy, it may contain Cu or Zn as an additive element other than Sn. Examples of the atomic concentration of the additive element include 0.1 atomic% or more and 50 atomic% or less, and further, 1 atomic% or more and 30 atomic% or less.

第一層１２１の厚さは、得られる電気接点材料１における第二金属層２２の厚さに大きく影響する。第一層１２１の厚さは、３．５μｍ以上５μｍ以下とする。第一層１２１の厚さを３．５μｍ以上とすることで、第二金属層２２の平均厚さが厚くなり易く、酸化物層３０側へのＣｕの拡散を抑制し易い。一方、第一層１２１の厚さを５μｍ以下とすることで、金属層２０の厚肉化を抑制できる。また、第一層１２１の厚さを５μｍ以下とすることで、金属層２０を形成する際の長時間化を抑制できる。第一層１２１の厚さは、更に３．５μｍ以上４．５μｍ以下、特に３．５μｍ以上４．０μｍ以下が挙げられる。第一層１２１の厚さは、例えば、めっき時の電流や時間によって所望の厚さとできる。 The thickness of the first layer 121 greatly affects the thickness of the second metal layer 22 in the obtained electrical contact material 1. The thickness of the first layer 121 is 3.5 μm or more and 5 μm or less. By setting the thickness of the first layer 121 to 3.5 μm or more, the average thickness of the second metal layer 22 tends to increase, and the diffusion of Cu toward the oxide layer 30 side tends to be suppressed. On the other hand, by setting the thickness of the first layer 121 to 5 μm or less, it is possible to suppress the thickening of the metal layer 20. Further, by setting the thickness of the first layer 121 to 5 μm or less, it is possible to suppress a long time when forming the metal layer 20. The thickness of the first layer 121 further includes 3.5 μm or more and 4.5 μm or less, particularly 3.5 μm or more and 4.0 μm or less. The thickness of the first layer 121 can be set to a desired thickness depending on, for example, the current and time during plating.

（第二層）
第二層１２２は、第一層１２１と第三層１２３の積層の順番が決まると一意的に決まり、第一層１２１の表面に設けられる。第二層１２２は、Ｚｎ又はＺｎ合金からなる。第二層１２２がＺｎ合金からなる場合、Ｚｎ以外の添加元素としてＳｎを含むことが挙げられる。添加元素の原子濃度としては、０．１原子％以上５０原子％以下が挙げられ、更に１原子％以上３０原子％以下が挙げられる。 (Second layer)
The second layer 122 is uniquely determined when the stacking order of the first layer 121 and the third layer 123 is determined, and is provided on the surface of the first layer 121. The second layer 122 is made of Zn or a Zn alloy. When the second layer 122 is made of a Zn alloy, Sn may be contained as an additive element other than Zn. Examples of the atomic concentration of the additive element include 0.1 atomic% or more and 50 atomic% or less, and further, 1 atomic% or more and 30 atomic% or less.

第二層１２２の厚さは、０．１μｍ以上０．６μｍ以下とする。第二層１２２の厚さを０．１μｍ以上とすることで、酸化物層３０中にＺｎを含有させ易く、基材１１０の酸化を抑制し易い。一方、第二層１２２の厚さを０．６μｍ以下とすることで、酸化物層３０にＳｎやＺｎを含有させ易く、Ｃｕを含有させ難い。第二層１２２の厚さは、更に０．２μｍ以上０．５μｍ以下、特に０．２μｍ以上０．４μｍ以下が挙げられる。第二層１２２の厚さは、例えば、めっき時の電流や時間によって所望の厚さとできる。 The thickness of the second layer 122 is 0.1 μm or more and 0.6 μm or less. By setting the thickness of the second layer 122 to 0.1 μm or more, Zn can be easily contained in the oxide layer 30, and oxidation of the base material 110 can be easily suppressed. On the other hand, when the thickness of the second layer 122 is 0.6 μm or less, Sn and Zn are likely to be contained in the oxide layer 30, and Cu is difficult to be contained. The thickness of the second layer 122 further includes 0.2 μm or more and 0.5 μm or less, particularly 0.2 μm or more and 0.4 μm or less. The thickness of the second layer 122 can be set to a desired thickness depending on, for example, the current and time during plating.

（第三層）
第三層１２３は、後述する熱処理により酸化し難いように、第二層１２２の表面に設けられる。第三層１２３の構成元素は、第一層１２１の構成元素と反応する。この反応によって、基材１１０の構成元素が、得られる電気接点材料１における表層（酸化物層３０）側へ過剰に拡散することを抑制できると推測される。第三層１２３は、被覆層１２０の最表層である。第三層１２３は、Ｃｕ又はＣｕ合金からなる。第三層１２３がＣｕ合金からなる場合、Ｃｕ以外の添加元素としてＳｎを含むことが挙げられる。添加元素の原子濃度としては、０．１原子％以上５０原子％以下が挙げられ、更に１原子％以上３０原子％以下が挙げられる。 (Third layer)
The third layer 123 is provided on the surface of the second layer 122 so as not to be easily oxidized by the heat treatment described later. The constituent elements of the third layer 123 react with the constituent elements of the first layer 121. It is presumed that this reaction can prevent the constituent elements of the base material 110 from being excessively diffused toward the surface layer (oxide layer 30) of the obtained electrical contact material 1. The third layer 123 is the outermost layer of the covering layer 120. The third layer 123 is made of Cu or a Cu alloy. When the third layer 123 is made of a Cu alloy, Sn may be contained as an additive element other than Cu. Examples of the atomic concentration of the additive element include 0.1 atomic% or more and 50 atomic% or less, and further, 1 atomic% or more and 30 atomic% or less.

第三層１２３の厚さは、０．０５μｍ以上０．４μｍ以下とする。第三層１２３の厚さを０．０５μｍ以上とすることで、酸化物層３０を形成し、基材１１０の酸化を抑制し易い。一方、第三層１２３の厚さを０．４μｍ以下とすることで、酸化物層３０にＳｎやＺｎを含有させ易く、Ｃｕを含有させ難い。第三層１２３の厚さは、更に０．１μｍ以上０．４μｍ以下、特に０．２μｍ以上０．４μｍ以下が挙げられる。第三層１２３の厚さは、例えば、めっき時の電流や時間によって所望の厚さとできる。 The thickness of the third layer 123 shall be 0.05 μm or more and 0.4 μm or less. By setting the thickness of the third layer 123 to 0.05 μm or more, the oxide layer 30 is formed and the oxidation of the base material 110 can be easily suppressed. On the other hand, when the thickness of the third layer 123 is 0.4 μm or less, Sn and Zn are likely to be contained in the oxide layer 30, and Cu is difficult to be contained. Further, the thickness of the third layer 123 is 0.1 μm or more and 0.4 μm or less, particularly 0.2 μm or more and 0.4 μm or less. The thickness of the third layer 123 can be set to a desired thickness depending on, for example, the current and time during plating.

〔熱処理工程〕
熱処理工程では、上記めっき工程後、被覆材料１００に熱処理を施す。熱処理は、酸素雰囲気中で行う。また、熱処理は、２３２℃以上５００℃以下の温度で行う。熱処理温度を２３２℃以上とすることで、Ｓｎを液相状態とでき、酸化物層３０にＳｎやＺｎを含有させ易く、Ｃｕを含有させ難い。一方、熱処理温度を５００℃以下とすることで、酸化物層３０側にＣｕの原子濃度がＳｎの原子濃度よりも十分に小さい第二金属層２２を形成し易く、酸化物層３０側へのＣｕの拡散を抑制し易い。熱処理温度は、更に２４０℃以上４５０℃以下、特に２５０℃以上４００℃以下が挙げられる。熱処理の保持時間は、１秒以上５分以下とすることが挙げられる。熱処理の保持時間を１秒以上とすることで、Ｓｎを液相状態とでき、酸化物層３０にＳｎやＺｎを含有させ易く、Ｃｕを含有させ難い。一方、熱処理の保持時間を５分以下とすることで、酸化物層３０側にＣｕの原子濃度がＳｎの原子濃度よりも十分に小さい第二金属層２２を形成し易く、酸化物層３０側へのＣｕの拡散を抑制し易い。熱処理の保持時間は、更に２秒以上４分以下、特に３秒以上３分以下が挙げられる。 [Heat treatment process]
In the heat treatment step, the coating material 100 is heat-treated after the plating step. The heat treatment is performed in an oxygen atmosphere. The heat treatment is performed at a temperature of 232 ° C. or higher and 500 ° C. or lower. By setting the heat treatment temperature to 232 ° C. or higher, Sn can be brought into a liquid phase state, and Sn and Zn are likely to be contained in the oxide layer 30, and Cu is difficult to be contained. On the other hand, when the heat treatment temperature is set to 500 ° C. or lower, it is easy to form the second metal layer 22 on the oxide layer 30 side in which the atomic concentration of Cu is sufficiently smaller than the atomic concentration of Sn, and the oxide layer 30 side is easily formed. It is easy to suppress the diffusion of Cu. Further, the heat treatment temperature is 240 ° C. or higher and 450 ° C. or lower, particularly 250 ° C. or higher and 400 ° C. or lower. The holding time of the heat treatment may be 1 second or more and 5 minutes or less. By setting the holding time of the heat treatment to 1 second or more, Sn can be put into a liquid phase state, and Sn and Zn are easily contained in the oxide layer 30, and Cu is difficult to be contained. On the other hand, by setting the heat treatment holding time to 5 minutes or less, it is easy to form the second metal layer 22 on the oxide layer 30 side in which the atomic concentration of Cu is sufficiently smaller than the atomic concentration of Sn, and the oxide layer 30 side. It is easy to suppress the diffusion of Cu into. The holding time of the heat treatment further includes 2 seconds or more and 4 minutes or less, particularly 3 seconds or more and 3 minutes or less.

熱処理は、めっき工程後１４日以内に行うことが挙げられる。めっき工程後の被覆材料１００は、被覆層１２０を構成する第一層１２１、第二層１２２、及び第三層１２３が経時的に合金化反応を起こす。めっき工程後１４日以内に熱処理を行うことで、第一層１２１、第二層１２２、及び第三層１２３の間で合金を形成する前に熱処理を行うことができる。よって、Ｓｎの融点以上の温度で熱処理を行うことで、液相状態のＳｎと、ＺｎやＣｕとの反応を適切に行える。この反応によって、最表面に酸化物層３０を備えると共に、酸化物層３０側に第二金属層２２を有する金属層２０を備える電気接点材料１を得ることができる。第二金属層２２は、Ｃｕの原子濃度がＳｎの原子濃度よりも十分に小さい層である。めっき工程後の熱処理までの時間は、短いほど被覆層１２０の合金化を抑制し易い。そのため、めっき工程後の熱処理までの時間は、更に１０日以内、５日以内、２日以内、特に１日以内が挙げられる。 The heat treatment may be performed within 14 days after the plating process. In the coating material 100 after the plating step, the first layer 121, the second layer 122, and the third layer 123 constituting the coating layer 120 undergo an alloying reaction over time. By performing the heat treatment within 14 days after the plating step, the heat treatment can be performed before forming the alloy between the first layer 121, the second layer 122, and the third layer 123. Therefore, by performing the heat treatment at a temperature equal to or higher than the melting point of Sn, the reaction between Sn in the liquid phase state and Zn or Cu can be appropriately performed. By this reaction, an electric contact material 1 having an oxide layer 30 on the outermost surface and a metal layer 20 having a second metal layer 22 on the oxide layer 30 side can be obtained. The second metal layer 22 is a layer in which the atomic concentration of Cu is sufficiently smaller than the atomic concentration of Sn. The shorter the time until the heat treatment after the plating step, the easier it is to suppress the alloying of the coating layer 120. Therefore, the time until the heat treatment after the plating step is further 10 days or less, 5 days or less, 2 days or less, particularly 1 day or less.

≪効果≫
実施形態に係る電気接点材料１は、酸化物層３０の直下において、Ｓｎの原子濃度に対するＣｕの原子濃度の比率が１．４未満を満たす。そのため、上記電気接点材料１は、酸化物層３０にＣｕの酸化物が形成され難い。Ｃｕの酸化物が少ない酸化物層３０は、導電性を確保し易い。よって、上記電気接点材料１は、最表面に酸化物層３０が存在する状態であっても、導電性の酸化物層３０及び金属層２０を介して、基材１０と相手材との間で良好な電気的接続を確保できる。従って、上記電気接点材料１は、相手材との接触圧力が小さい場合であっても、接触抵抗の上昇を抑制できる。 ≪Effect≫
In the electrical contact material 1 according to the embodiment, the ratio of the atomic concentration of Cu to the atomic concentration of Sn is less than 1.4 immediately below the oxide layer 30. Therefore, in the electrical contact material 1, it is difficult for Cu oxide to be formed in the oxide layer 30. The oxide layer 30 having a small amount of Cu oxide can easily secure conductivity. Therefore, in the electrical contact material 1, even when the oxide layer 30 is present on the outermost surface, the base material 10 and the mating material can be separated from each other via the conductive oxide layer 30 and the metal layer 20. Good electrical connection can be ensured. Therefore, the electrical contact material 1 can suppress an increase in contact resistance even when the contact pressure with the mating material is small.

実施形態に係る電気接点材料の製造方法では、基材１１０側から順に、Ｓｎを含む金属からなる第一層１２１、Ｚｎを含む金属からなる第二層１２２、及びＣｕを含む金属からなる第三層１２３を被覆した被覆材料１００を作製する。このとき、各層１２１，１２２，１２３を、特定の範囲の厚さで被覆する。そして、その被覆材料１００に特定の範囲の温度で熱処理を施す。そうすることで、基材１１０（基材１０）の表面にＳｎ、Ｚｎ、及びＣｕを含む合金からなる金属層２０を形成でき、その金属層２０の表面に形成される酸化物層３０の直下において、Ｓｎの原子濃度に対するＣｕの原子濃度の比率を、１．４未満とできる。 In the method for producing an electrical contact material according to the embodiment, in order from the base material 110 side, a first layer 121 made of a metal containing Sn, a second layer 122 made of a metal containing Zn, and a third layer made of a metal containing Cu are used. A coating material 100 coated with the layer 123 is produced. At this time, each layer 121, 122, 123 is covered with a thickness in a specific range. Then, the coating material 100 is heat-treated at a temperature in a specific range. By doing so, a metal layer 20 made of an alloy containing Sn, Zn, and Cu can be formed on the surface of the base material 110 (base material 10), and the metal layer 20 is directly below the oxide layer 30 formed on the surface of the metal layer 20. The ratio of the atomic concentration of Cu to the atomic concentration of Sn can be less than 1.4.

［試験例１］
基材と、基材の表面に設けられる金属層と、金属層の表面に設けられる酸化物層とを備える電気接点材料を作製した。そして、電気接点材料について、酸化物層の直下におけるＳｎとＣｕの原子濃度の比率、及び接触抵抗を調べた。 [Test Example 1]
An electrical contact material including a base material, a metal layer provided on the surface of the base material, and an oxide layer provided on the surface of the metal layer was produced. Then, for the electrical contact material, the ratio of the atomic concentrations of Sn and Cu directly under the oxide layer and the contact resistance were investigated.

≪試料の作製≫
基材の表面に、基材側から順に、有機酸Ｓｎめっき（第一層）、硫酸Ｚｎめっき（第二層）、及びピロリン酸Ｃｕめっき（第三層）を電気めっきにより施した。各層の厚さは、表１に示す。基材には、Ｃｕからなる金属板の表面に、０．２μｍの硫酸銅めっきを施した被覆金属板を用いた。基材の表面にめっき処理を施した後、めっき付き基板に熱処理を施した。熱処理の条件は、表１に示す。なお、熱処理の保持時間は、いずれも３分とした。表１における「熱処理までの時間」は、めっき終了直後から熱処理を行うまでの時間である。 ≪Preparation of sample≫
The surface of the base material was electroplated with organic acid Sn plating (first layer), sulfuric acid Zn plating (second layer), and pyrophosphate Cu plating (third layer) in order from the base material side. The thickness of each layer is shown in Table 1. As the base material, a coated metal plate in which the surface of a metal plate made of Cu was plated with 0.2 μm copper sulfate was used. After plating the surface of the base material, the plated substrate was heat-treated. The heat treatment conditions are shown in Table 1. The heat treatment holding time was set to 3 minutes in each case. The "time until heat treatment" in Table 1 is the time from immediately after the completion of plating to the heat treatment.

Figure 2021004405
Figure 2021004405

≪組成分析≫
作製した各試料の電気接点材料について、Ｘ線光電子分光分析を用いて表層の酸化物層の組成分析を行った。その結果、試料Ｎｏ．１−１〜試料Ｎｏ．１−７は、Ｚｎ、Ｃｕ、及びＳｎを含む酸化物層が形成されていることがわかった。また、試料Ｎｏ．１−１〜試料Ｎｏ．１−７について、蛍光Ｘ線分析装置を用いて酸化物層の下層の組成分析を行った。その結果、酸化物層の下層には、主にＳｎからなる層（第二金属層）と、更にその下層には、主に（Ｃｕ，Ｚｎ）６Ｓｎ５からなる金属間化合物を含有する層（第一金属層）とが形成されていることがわかった。 ≪Composition analysis≫
The composition of the oxide layer on the surface of each of the prepared electrical contact materials was analyzed using X-ray photoelectron spectroscopy. As a result, the sample No. 1-1-1 Sample No. It was found that in 1-7, an oxide layer containing Zn, Cu, and Sn was formed. In addition, sample No. 1-1-1 Sample No. For 1-7, the composition of the lower layer of the oxide layer was analyzed using a fluorescent X-ray analyzer. As a result, the lower layer of the oxide layer contains a layer mainly composed of Sn (second metal layer), and the lower layer further contains an intermetallic compound mainly composed of (Cu, Zn) 6 Sn 5. It was found that (first metal layer) was formed.

≪酸化物層≫
作製した各試料の電気接点材料について、酸化物層の厚さ、及び酸化物層中の各元素の原子濃度を、Ｘ線光電子分光分析を用いて調べた。酸化物層の厚さ、及び酸化物層中の各元素の原子濃度を表２に示す。なお、酸化物層中にはＯ、Ｚｎ、Ｃｕ、及びＳｎ以外に不純物が含有されていたが、その不純物は表中からは除外している。 ≪Oxide layer≫
For the electrical contact material of each of the prepared samples, the thickness of the oxide layer and the atomic concentration of each element in the oxide layer were examined by using X-ray photoelectron spectroscopy. Table 2 shows the thickness of the oxide layer and the atomic concentration of each element in the oxide layer. The oxide layer contained impurities other than O, Zn, Cu, and Sn, but the impurities were excluded from the table.

≪酸化物層の直下≫
作製した各試料の電気接点材料について、酸化物層の直下におけるＳｎの原子濃度に対するＣｕの原子濃度の比率（原子濃度比Ｃｕ／Ｓｎ）を、Ｘ線光電子分光分析を用いて調べた。なお、酸化物層の直下は、酸化物層と第二金属層との界面からの第二金属層側のＳｉＯ２のスパッタリングレート換算で０．０５μｍ以下の範囲とした。その結果を表２に併せて示す。 ≪Directly below the oxide layer≫
For the electrical contact material of each of the prepared samples, the ratio of the atomic concentration of Cu to the atomic concentration of Sn immediately under the oxide layer (atomic concentration ratio Cu / Sn) was examined by using X-ray photoelectron spectroscopy. The area directly below the oxide layer was set to a range of 0.05 μm or less in terms of the sputtering rate of SiO 2 on the second metal layer side from the interface between the oxide layer and the second metal layer. The results are also shown in Table 2.

≪第二金属層及び第一金属層≫
作製した各試料の電気接点材料について、酸化物層の下層の第二金属層及び第一金属層の厚さを調べた。第二金属層の厚さは、蛍光Ｘ線膜厚計を用いて以下のように求めた。まず、第二金属層及び第一金属層の全体における特定面積（０．０３ｍｍ２）中のＳｎの含有量を蛍光Ｘ線分析膜厚計により測定した。その後、水酸化ナトリウム、Ｐ−ニトリルフェノール、及び蒸留水から成る混合液を用いて第二金属層のみをエッチングで除去した。そして、残存した第一金属層における上記特定面積中のＳｎの含有量を蛍光Ｘ線分析膜厚計により測定した。第二金属層の厚さは、それぞれ測定した各層におけるＳｎの含有量の差から算出した。第一金属層の厚さは、第二金属層を除去した後に、Ｓｎの含有量を蛍光Ｘ線分析膜厚計により測定し、第一金属層の組成、密度、及び上記特定面積から換算した。その結果を表２に併せて示す。 ≪Second metal layer and first metal layer≫
The thicknesses of the second metal layer and the first metal layer under the oxide layer were examined for the electrical contact materials of each of the prepared samples. The thickness of the second metal layer was determined as follows using a fluorescent X-ray film thickness meter. First, the Sn content in the specific area (0.03 mm 2 ) of the second metal layer and the first metal layer as a whole was measured by a fluorescent X-ray analysis film thickness meter. Then, only the second metal layer was removed by etching using a mixed solution consisting of sodium hydroxide, P-nitrile phenol, and distilled water. Then, the Sn content in the specific area in the remaining first metal layer was measured by a fluorescent X-ray analysis film thickness meter. The thickness of the second metal layer was calculated from the difference in Sn content in each measured layer. The thickness of the first metal layer was calculated from the composition, density, and the specific area of the first metal layer by measuring the Sn content with a fluorescent X-ray analysis film thickness meter after removing the second metal layer. .. The results are also shown in Table 2.

≪接触抵抗≫
作製した各試料の電気接点材料について、金めっきした半径１ｍｍの球状の圧子を１Ｎの荷重で接触させ、４端子法の抵抗測定装置を用いて測定した。接触抵抗は、熱処理後、常温に冷却したままの試料の接触抵抗（初期抵抗）と、１６０℃で１２０分保持した後の試料の接触抵抗（耐久後抵抗）とを測定した。その結果を表２に併せて示す。 ≪Contact resistance≫
The electrical contact material of each of the prepared samples was contacted with a gold-plated spherical indenter having a radius of 1 mm with a load of 1 N, and measured using a resistance measuring device of the 4-terminal method. As the contact resistance, the contact resistance (initial resistance) of the sample kept cooled to room temperature after the heat treatment and the contact resistance (post-durability resistance) of the sample after holding at 160 ° C. for 120 minutes were measured. The results are also shown in Table 2.

Figure 2021004405
Figure 2021004405

表１及び表２に示すように、試料Ｎｏ．１−１〜試料Ｎｏ．１−７は、原子濃度比Ｃｕ／Ｓｎが１．４未満を満たしている。これは、試料Ｎｏ．１−１〜試料Ｎｏ．１−７は、電気接点材料の製造過程において、基材側から順に、第一層、第二層、及び第三層を特定の厚さとなるようにめっき処理を施し、その後２７０℃又は３００℃で熱処理を施したからと考えられる。具体的な各層の厚さは、第一層が０．５μｍ以上５μｍ以下、第二層が０．１μｍ以上０．６μｍ以下、第三層が０．０５μｍ以上０．４μｍ以下としている。 As shown in Table 1 and Table 2, the sample No. 1-1-1 Sample No. 1-7 satisfies the atomic concentration ratio Cu / Sn of less than 1.4. This is the sample No. 1-1-1 Sample No. In 1-7, in the manufacturing process of the electrical contact material, the first layer, the second layer, and the third layer are plated so as to have a specific thickness in order from the base material side, and then 270 ° C. or 300 ° C. is applied. It is probable that it was heat-treated in. Specifically, the thickness of each layer is 0.5 μm or more and 5 μm or less for the first layer, 0.1 μm or more and 0.6 μm or less for the second layer, and 0.05 μm or more and 0.4 μm or less for the third layer.

基材上に、第一層、第二層、及び第三層からなる被覆層を被覆した被覆材料は、経時的に合金化反応を起こす。一方で、上記被覆材料に熱処理を施すと、被覆材料の表面に酸化物層が形成される。このとき、各層を特定の厚さとし、かつ特定の温度で熱処理を施すことで、以下の現象が生じていると考えられる。上記特定の温度で熱処理を行うことで、Ｓｎが液相状態となる。Ｓｎめっきされた第一層が上記特定の厚さを有することで、第一層中のＳｎは、液相状態となり、酸化物層側に拡散される。このＳｎによって、酸化物層にＳｎの酸化物が形成されると共に、酸化物層の直下に主にＳｎからなる第二金属層が形成されると考えられる。また、Ｚｎめっきされた第二層が上記特定の厚さを有することで、第二層中のＺｎも、Ｓｎと同様に、酸化物層側に拡散され、酸化物層にＺｎの酸化物が形成されると考えられる。しかし、上記特定の温度では、Ｚｎは液相状態となり難く、第二金属層には、Ｚｎが含まれたとしても微量であると考えられる。一方、Ｃｕめっきされた第三層が上記特定の厚さを有することで、第三層中のＣｕは、酸化物層側に拡散され難く、第二金属層中には、Ｃｕが含まれたとしても微量であり、かつ酸化物層中に形成されるＣｕの酸化物も少ないと考えられる。以上より、試料Ｎｏ．１−１〜試料Ｎｏ．１−７は、基材の表面に、主に（Ｃｕ，Ｚｎ）６Ｓｎ５からなる金属間化合物を含有する第一金属層が形成され、最表面に、めっきした各層の構成元素を含有する酸化物層が形成されたと考えられる。なお、（Ｃｕ，Ｚｎ）６Ｓｎ５とは、主にＣｕ６Ｓｎ５であるが、一部のＣｕがＺｎに置き換わっていることを意味する。このとき、試料Ｎｏ．１−１〜試料Ｎｏ．１−７は、液相状態のＳｎによって、第一金属層と酸化物層との間に、主にＳｎからなる第二金属層が形成され、酸化物層の直下における原子濃度比Ｃｕ／Ｓｎが０．２２以下と小さくなったと考えられる。 A coating material in which a coating layer composed of a first layer, a second layer, and a third layer is coated on a base material causes an alloying reaction over time. On the other hand, when the coating material is heat-treated, an oxide layer is formed on the surface of the coating material. At this time, it is considered that the following phenomenon occurs by making each layer a specific thickness and performing heat treatment at a specific temperature. By performing the heat treatment at the above specific temperature, Sn becomes a liquid phase state. When the Sn-plated first layer has the above-mentioned specific thickness, Sn in the first layer is in a liquid phase state and is diffused to the oxide layer side. It is considered that this Sn forms an oxide of Sn in the oxide layer and a second metal layer mainly composed of Sn is formed directly under the oxide layer. Further, since the Zn-plated second layer has the above-mentioned specific thickness, Zn in the second layer is also diffused to the oxide layer side in the same manner as Sn, and the oxide of Zn is contained in the oxide layer. It is thought to be formed. However, at the above specific temperature, Zn is unlikely to be in a liquid phase state, and it is considered that even if Zn is contained in the second metal layer, it is in a trace amount. On the other hand, since the Cu-plated third layer has the above-mentioned specific thickness, Cu in the third layer is hard to be diffused to the oxide layer side, and Cu is contained in the second metal layer. However, it is considered that the amount is very small and the amount of Cu oxide formed in the oxide layer is also small. From the above, the sample No. 1-1-1 Sample No. In 1-7, a first metal layer containing an intermetallic compound mainly composed of (Cu, Zn) 6 Sn 5 is formed on the surface of the base material, and the outermost surface contains the constituent elements of each plated layer. It is considered that an oxide layer was formed. Note that (Cu, Zn) 6 Sn 5 is mainly Cu 6 Sn 5 , but means that some Cu is replaced with Zn. At this time, the sample No. 1-1-1 Sample No. In 1-7, a second metal layer mainly composed of Sn is formed between the first metal layer and the oxide layer by Sn in the liquid phase state, and the atomic concentration ratio Cu / Sn directly under the oxide layer is Cu / Sn. Is considered to have decreased to 0.22 or less.

酸化物層の直下における原子濃度比Ｃｕ／Ｓｎが１．４未満であることで、酸化物層にＣｕの酸化物が形成され難い。銅の酸化物が少ない酸化物層は、低抵抗で導電性を確保し易い。そのため、試料Ｎｏ．１−１〜試料Ｎｏ．１−７は、金属層の表面に酸化物層が存在する状態であっても、初期抵抗と耐久後抵抗とがほぼ同じであり、接触抵抗の上昇を抑制できたと考えられる。 When the atomic concentration ratio Cu / Sn immediately below the oxide layer is less than 1.4, it is difficult for Cu oxide to be formed in the oxide layer. An oxide layer containing a small amount of copper oxide has low resistance and is easy to secure conductivity. Therefore, the sample No. 1-1-1 Sample No. In 1-7, even when the oxide layer was present on the surface of the metal layer, the initial resistance and the post-durability resistance were almost the same, and it is considered that the increase in contact resistance could be suppressed.

一方、試料Ｎｏ．１−１５及び試料Ｎｏ．１−１６は、原子濃度比Ｃｕ／Ｓｎが１．４以上と大きい。これは、電気接点材料の製造過程において、第一層の厚さが薄いからと考えらえる。第一層の厚さが薄いことで、第一層中のＳｎが酸化物層側に拡散され難く、相対的に酸化物層の直下のＣｕ量が増加したと考えられる。酸化物層の直下における原子濃度比Ｃｕ／Ｓｎが１．４以上と大きいことで、酸化物層にＣｕの酸化物が形成され易い。そのため、試料Ｎｏ．１−１５及び試料Ｎｏ．１−１６は、初期抵抗に比較して耐久後抵抗が増加したと考えられる。特に、第一層の厚さがより薄い試料Ｎｏ．１−１５は、酸化物層の下層に第二金属層は形成されず、かつ酸化物層中にＳｎは含有されなかった。よって、試料Ｎｏ．１−１５は、初期抵抗も大きくなっていた。 On the other hand, sample No. 1-15 and sample No. In 1-16, the atomic concentration ratio Cu / Sn is as large as 1.4 or more. This is considered to be because the thickness of the first layer is thin in the manufacturing process of the electrical contact material. It is considered that because the thickness of the first layer is thin, Sn in the first layer is less likely to be diffused to the oxide layer side, and the amount of Cu directly under the oxide layer is relatively increased. Since the atomic concentration ratio Cu / Sn immediately below the oxide layer is as large as 1.4 or more, Cu oxide is likely to be formed in the oxide layer. Therefore, the sample No. 1-15 and sample No. In 1-16, it is considered that the resistance after durability increased as compared with the initial resistance. In particular, the sample No. in which the thickness of the first layer is thinner. In 1-15, the second metal layer was not formed in the lower layer of the oxide layer, and Sn was not contained in the oxide layer. Therefore, the sample No. In 1-15, the initial resistance was also large.

試料Ｎｏ．１−１４は、原子濃度比Ｃｕ／Ｓｎが４と非常に大きい。これは、電気接点材料の製造過程において、第二層の厚さが厚いからと考えらえる。第二層の厚さが厚いことで、第一層中のＳｎが酸化物層側に拡散され難く、相対的に酸化物層の直下のＣｕ量が増加したと考えられる。実際に、酸化物層中にＳｎは含有されなかった。よって、試料Ｎｏ．１−１４は、初期抵抗も大きくなっていた。 Sample No. 1-14 has a very large atomic concentration ratio Cu / Sn of 4. It is considered that this is because the thickness of the second layer is thick in the manufacturing process of the electrical contact material. It is considered that because the thickness of the second layer is thick, Sn in the first layer is less likely to be diffused to the oxide layer side, and the amount of Cu directly under the oxide layer is relatively increased. In fact, Sn was not contained in the oxide layer. Therefore, the sample No. The initial resistance of 1-14 was also large.

試料Ｎｏ．１−１２は、原子濃度比Ｃｕ／Ｓｎが１．７２と大きい。これは、電気接点材料の製造過程において、第三層を設けていないからと考えらえる。第三層を設けていないことで、第一層中のＳｎと反応する元素がなく、基材１１０の構成元素（本例ではＣｕ）が酸化物層側に拡散され易く、酸化物層の直下に基材に由来するＣｕ量が増加したと考えられる。よって、試料Ｎｏ．１−１２は、初期抵抗に比較して耐久後抵抗が増加したと考えられる。 Sample No. 1-12 has a large atomic concentration ratio Cu / Sn of 1.72. It can be considered that this is because the third layer is not provided in the manufacturing process of the electrical contact material. Since the third layer is not provided, there is no element that reacts with Sn in the first layer, and the constituent elements (Cu in this example) of the base material 110 are easily diffused to the oxide layer side, and is directly under the oxide layer. It is considered that the amount of Cu derived from the base material increased. Therefore, the sample No. It is considered that the resistance after durability increased in 1-12 as compared with the initial resistance.

試料Ｎｏ．１−１３は、原子濃度比Ｃｕ／Ｓｎが１．４１と大きい。これは、電気接点材料の製造過程において、第三層の厚さが厚いからと考えらえる。第三層の厚さが厚いことで、第三層中のＣｕが酸化物層側に拡散され易く、相対的に酸化物層の直下のＳｎ量が減少したと考えられる。酸化物層の直下における原子濃度比Ｃｕ／Ｓｎが１．４以上と大きいことで、酸化物層にＣｕの酸化物が形成され易い。実際に、酸化物層中のＣｕの原子濃度は、５０．７原子％と非常に多くなっている。そのため、試料Ｎｏ．１−１３は、初期抵抗に比較して耐久後抵抗が増加したと考えられる。また、試料Ｎｏ．１−１３は、酸化物層中にＳｎは含有されなかった。よって、試料Ｎｏ．１−１３は、初期抵抗も大きくなっていた。 Sample No. In 1-13, the atomic concentration ratio Cu / Sn is as large as 1.41. It is considered that this is because the thickness of the third layer is thick in the manufacturing process of the electrical contact material. It is considered that because the thickness of the third layer is thick, Cu in the third layer is easily diffused to the oxide layer side, and the amount of Sn immediately below the oxide layer is relatively reduced. Since the atomic concentration ratio Cu / Sn immediately below the oxide layer is as large as 1.4 or more, Cu oxide is likely to be formed in the oxide layer. In fact, the atomic concentration of Cu in the oxide layer is as high as 50.7 atomic%. Therefore, the sample No. In 1-13, it is considered that the resistance after durability increased as compared with the initial resistance. In addition, sample No. In 1-13, Sn was not contained in the oxide layer. Therefore, the sample No. In 1-13, the initial resistance was also large.

試料Ｎｏ．１−１１は、原子濃度比Ｃｕ／Ｓｎが１．４未満を満たしている。しかし、試料Ｎｏ．１−１１は、初期抵抗が大きく、また初期抵抗に対する耐久後抵抗も大きい。これは、電気接点材料の製造過程において、第二層を設けていないからと考えられる。第二層を設けていないことで、酸化物層中にＺｎが含有されず、酸化物層の抵抗が増加したと考えられる。 Sample No. 1-11 satisfies the atomic concentration ratio Cu / Sn of less than 1.4. However, sample No. 1-11 has a large initial resistance and also a large post-durability resistance to the initial resistance. It is considered that this is because the second layer is not provided in the manufacturing process of the electrical contact material. It is considered that Zn was not contained in the oxide layer and the resistance of the oxide layer increased because the second layer was not provided.

１ 電気接点材料
１０ 基材
２０ 金属層、２１ 第一金属層、２２ 第二金属層
３０ 酸化物層
１００ 被覆材料
１１０ 基材
１２０ 被覆層、１２１ 第一層、１２２ 第二層、１２３ 第三層
２００ 端子金具
２１０ ワイヤバレル部、２２０ インシュレーションバレル部
２３０ 嵌合部、２３１ 箱部、２３２、２３３ 弾性片
３００ 電線、３１０ 導体、３２０ 絶縁層 1 Electrical contact material 10 Base material 20 Metal layer, 21 First metal layer, 22 Second metal layer 30 Oxide layer 100 Coating material 110 Base material 120 Coating layer, 121 First layer, 122 Second layer, 123 Third layer 200 Terminal metal fittings 210 Wire barrel part, 220 Insulation barrel part 230 Fitting part, 231 Box part, 232, 233 Elastic pieces 300 Electric wire, 310 conductor, 320 Insulation layer

Claims (10)

金属からなる基材と、
前記基材の表面に設けられる金属層と、
前記金属層の表面に設けられる酸化物層とを備え、
前記金属層は、亜鉛、銅、及びスズを含む金属からなり、
前記酸化物層は、亜鉛、銅、及びスズを含む酸化物からなり、
前記酸化物層の直下において、スズの原子濃度に対する銅の原子濃度の比率が１．４未満である、
電気接点材料。 A base material made of metal and
A metal layer provided on the surface of the base material and
It is provided with an oxide layer provided on the surface of the metal layer.
The metal layer is made of a metal containing zinc, copper, and tin.
The oxide layer is composed of oxides containing zinc, copper, and tin.
Immediately below the oxide layer, the ratio of the atomic concentration of copper to the atomic concentration of tin is less than 1.4.
Electrical contact material. 前記酸化物層中の各元素の原子濃度は、
酸素が０原子％超７０原子％以下、
亜鉛が０原子％超７０原子％以下、
銅が０原子％超３０原子％以下、
スズが０原子％超３０原子％以下、である請求項１に記載の電気接点材料。 The atomic concentration of each element in the oxide layer is
Oxygen is more than 0 atomic% and 70 atomic% or less,
Zinc is more than 0 atomic% and 70 atomic% or less,
Copper is more than 0 atomic% and less than 30 atomic%,
The electrical contact material according to claim 1, wherein the tin content is more than 0 atomic% and 30 atomic% or less. 前記酸化物層の平均厚さは、１ｎｍ以上１０００ｎｍ以下である請求項１又は請求項２に記載の電気接点材料。 The electrical contact material according to claim 1 or 2, wherein the average thickness of the oxide layer is 1 nm or more and 1000 nm or less. 前記金属層は、
前記基材側に設けられる第一金属層と、
前記酸化物層側に設けられる第二金属層とを備え、
前記第一金属層は、亜鉛、銅、及びスズからなる群より選択される２種以上の元素を含む合金からなり、
前記第二金属層は、スズ又はスズ合金からなる請求項１から請求項３のいずれか１項に記載の電気接点材料。 The metal layer is
The first metal layer provided on the base material side and
A second metal layer provided on the oxide layer side is provided.
The first metal layer is composed of an alloy containing two or more elements selected from the group consisting of zinc, copper, and tin.
The electrical contact material according to any one of claims 1 to 3, wherein the second metal layer is made of tin or a tin alloy. 前記第一金属層の平均厚さは、０．１μｍ以上５μｍ以下である請求項４に記載の電気接点材料。 The electrical contact material according to claim 4, wherein the average thickness of the first metal layer is 0.1 μm or more and 5 μm or less. 前記第二金属層の平均厚さは、０．１μｍ以上５μｍ以下である請求項４又は請求項５に記載の電気接点材料。 The electrical contact material according to claim 4 or 5, wherein the average thickness of the second metal layer is 0.1 μm or more and 5 μm or less. 請求項１から請求項６のいずれか１項に記載の電気接点材料からなる、
端子金具。 The electrical contact material according to any one of claims 1 to 6.
Terminal bracket. 請求項７に記載の端子金具を備える、
コネクタ。 The terminal fitting according to claim 7 is provided.
connector. 電線と、
前記電線に取り付けられる請求項７に記載の端子金具、又は請求項８に記載のコネクタとを備える、
ワイヤーハーネス。 With electric wires
The terminal fitting according to claim 7 or the connector according to claim 8 is provided, which is attached to the electric wire.
Wire Harness. 基材の表面の少なくとも一部に、前記基材側から順に、第一層、第二層、及び第三層をめっきにより被覆した被覆材料を作製する工程と、
前記被覆材料に、酸素雰囲気中、２３２℃以上５００℃以下の温度で熱処理を施す工程とを備え、
前記被覆材料を作製する工程では、
前記第一層は、スズを含む金属からなり、
前記第二層は、亜鉛を含む金属からなり、
前記第三層は、銅を含む金属からなり、
前記第一層の厚さを３．５μｍ以上５μｍ以下、
前記第二層の厚さを０．１μｍ以上０．６μｍ以下、
前記第三層の厚さを０．０５μｍ以上０．４μｍ以下とする、
電気接点材料の製造方法。 A step of producing a coating material in which the first layer, the second layer, and the third layer are coated by plating on at least a part of the surface of the base material in order from the base material side.
The coating material is provided with a step of heat-treating the coating material at a temperature of 232 ° C. or higher and 500 ° C. or lower in an oxygen atmosphere.
In the step of producing the coating material,
The first layer is made of a metal containing tin and
The second layer is made of a metal containing zinc and
The third layer is made of a metal containing copper.
The thickness of the first layer is 3.5 μm or more and 5 μm or less.
The thickness of the second layer is 0.1 μm or more and 0.6 μm or less.
The thickness of the third layer is 0.05 μm or more and 0.4 μm or less.
Manufacturing method of electrical contact material.
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